CN101720350B

CN101720350B - Method for production of liquid fuel

Info

Publication number: CN101720350B
Application number: CN200880014266.4A
Authority: CN
Inventors: 关浩幸; 东正浩; 齐藤纯夫; 黑田隆三; 龟冈隆
Original assignee: GC CATALYSTS AND CHEMICALS LT; Nippon Oil Corp
Current assignee: GC CATALYSTS AND CHEMICALS LT; Eneos Corp
Priority date: 2007-05-01
Filing date: 2008-04-26
Publication date: 2014-01-22
Anticipated expiration: 2028-04-26
Also published as: US20100122935A1; WO2008139909A1; RU2451714C2; CN101720350A; DK2147964T3; JPWO2008139909A1; EP2147964A4; AU2008249251B2; JP5268177B2; EP2147964B1; EP2147964A1; RU2009144260A; US8366911B2; AU2008249251A1; MY149339A

Abstract

Disclosed is a method for producing a liquid fuel, which is characterized by comprising the steps of: hydrogenating a raw oil mainly composed of a paraffin-type hydrocarbon having 20 to 100 carbon atoms in the presence of a specific hydrogenation catalyst at a temperature of 200 to 350 DEG C, at a liquid hourly space velocity of 0.1 to 5.0 h<-1> and at a hydrogen partial pressure of 0.5 to 8 MPa to produce a processed oil; and fractionating the processed oil to produce an intermediate fraction which contains a light oil having a cetane value of 75 or greater and a pour point of -27.5 DEG C or lower at a yield of 55% or greater relative to the total mass of the raw oil.

Description

The manufacture method of liquid fuel

Technical field

The present invention relates to a kind of manufacture method of liquid fuel, described manufacture method can obtain the middle runnings as liquid fuel by usining the stock oil that paraffins is main component with high yield.

Background technology

At present, in the middle runnings being obtained by crude oil manufacture (being lam-oil and light oil), contain the environmental pollutants such as sulfide and aromatics, this becomes one of reason causing environmental pollution.Therefore, the manufacture method of known a kind of liquid fuel,, the hydrotreating catalyst of utilization carrier band platinum in the carrier that contains amorphous aluminum silicide (amorphous silica-alumina), to take the stock oil that the low paraffins of above-mentioned environmental pollutants content (paraffin hydrocarbon) is main component, carry out after hydrogen treatment, by its fractionation, obtain low, the environmental middle runnings of environmental pollutants content (for example patent documentation 1).In addition, the manufacture method of known a kind of liquid fuel also, the method is used the hydrotreating catalyst (for example patent documentation 2) of carrier band periodictable Ba family metal in the carrier that contains crystallized silicon aluminate.

Patent documentation 1: Unexamined Patent 6-41549 communique

Patent documentation 2: JP 2004-255241 communique

Summary of the invention

But, the hydrotreating catalyst of recording in patent documentation 1, although the selectivity to middle runnings in the hydrocracking of paraffins is good, but there is following problems, due to hydrocracking poor performance, so must or reduce the yield that liquid hourly space velocity (liquid hourly spacevelocity (LHSV)) is guaranteed middle runnings by rising temperature of reaction, cause energy expenditure to increase and productivity reduction.

On the other hand, the hydrotreating catalyst of recording in patent documentation 2 is compared with the catalyzer of the use amorphous aluminum silicide of recording in patent documentation 1, and hydrocracking performance is high, but exist isomerization performance low, cannot obtain with high yield the problem of middle runnings.

The present invention in view of the above fact and research obtains, object be to provide a kind of can be by take stock oil that the paraffins of carbonatoms 20～100 is main component to keep high de-agglomeration active and take the manufacture method of the liquid fuel that the light oil that contains in that high yield obtains middle runnings and this middle runnings is high characteristic.

The manufacture method of the liquid fuel of the present invention based on above-mentioned purpose is the manufacture method of liquid fuel as described below, that is, under the existence of hydrotreating catalyst, in temperature, be that 200～350 ℃, liquid hourly space velocity are 0.1～5.0h ^-1and under the hydrogen dividing potential drop condition that is 0.5～8MPa, to take the stock oil that the paraffins of carbonatoms 20～100 is main component, carry out hydrogen treatment, obtain processing after oil, this processing oil content is heated up in a steamer, the yield obtaining with respect to the total mass of above-mentioned raw materials oil is more than 55%, and it is more than 75 containing cetane value and yield point is the middle runnings of-27.5 ℃ of following light oil, wherein, the above-mentioned hydrotreating catalyst active metal composition that carrier band is formed by platinum or palladium in the carrier that contains amorphous solid acid and hyperstabilized y-type zeolite, the dehydrogenation with hydro carbons, isomerization performance, hydrocracking performance and Hydrogenation, the median size of described hyperstabilized y-type zeolite is 0.2～1.0 μ m, take standard y-type zeolite benchmark degree of crystallinity as 1.02～1.10 and specific surface area be 700～790m ²/ g.

Herein, the hyperstabilized y-type zeolite using in hydrotreating catalyst of the present invention is (following, also referred to as " USY zeolite ") be that median size is the fine particle of 0.2～1.0 μ m, and take standard y-type zeolite benchmark degree of crystallinity as 1.02～1.10 and specific surface area be 700～790m ²/ g, has advantages of that crystallinity is high, purity is high.

The median size of USY zeolite is measured and is obtained by electron microscope (SEM), for example, measure the maximum length of 100 offsprings, with its mean value, represents.The zeolite that the median size of USY zeolite is less than 0.2 μ m is difficult to form, and in addition, if median size surpasses 1.0 μ m, during for the hydrocracking of paraffins, has middle runnings excessive decomposition, the tendency that the yield of middle runnings reduces.

In the present invention, the degree of crystallinity of USY zeolite can be calculated as follows: (primary standard usually used as the degree of crystallinity of y-type zeolite is used to use Union Carbide SK-40 processed.Below, also referred to as " SK-40 ") as standard y-type zeolite benchmark, obtain total peak height (H) of (331) face, (511) face, (440) face, (533) face, (642) face and (555) face of X-ray diffraction and total peak height (H of the above-mentioned identical faces of SK-40 of the USY zeolite of mensuration ₀), the degree of crystallinity of SK-40 of take is 1, according to formula (1), calculates.It should be noted that, the degree of crystallinity of USY zeolite of the present invention is more than 1.02, be preferably more than 1.03, and be more preferably more than 1.05.

Degree of crystallinity=H/H ₀(1)

In addition, the specific surface area of USY zeolite of the present invention is to measure by BET method the value obtaining, and is 700m ²more than/g, be preferably 720m ²more than/g, be more preferably 750m ²more than/g, 780m more preferably ²more than/g, its in calculating on be limited to 790m ²/ g.

It should be noted that, the degree of crystallinity of the hyperstabilized y-type zeolite of current known median size within the scope of 0.2～1.0 μ m be less than 1.00 and/or specific surface area be less than 700m ²/ g, shows that crystallinity is low.

As the hydrotreated condition of stock oil, temperature is 200～350 ℃, is preferably 240～290 ℃, and liquid hourly space velocity is 0.1～5.0h ^-1, be preferably 0.5～2.0h ^-1, hydrogen dividing potential drop is 0.5～8MPa, be preferably 1.0～4.0MPa.

Herein, hydrotreated temperature during lower than 200 ℃, exists the isomerization reaction of paraffins to be difficult to the tendency occurring; If surpass 350 ℃, there is paraffins excessive decomposition, the tendency that the yield of middle runnings reduces.

It should be noted that so-called liquid hourly space velocity (LHSV.The volumetric flow rate of the stock oil of the per unit capacity of catalyst layer that liquid hourly space velocity) refers to catalyst filling under standard state (25 ℃, 101325Pa), " h ^-1" the expression time (and hour) inverse.Liquid hourly space velocity is lower than 0.1h ^-1time, there is paraffins excessive decomposition, the tendency that the yield of middle runnings reduces; If surpass 5.0h ^-1, exist the decomposition of paraffins to be difficult to occur, the tendency that the yield of middle runnings reduces.

In addition, hydrogen dividing potential drop during lower than 0.5MPa, exists hydrotreating catalyst that deteriorated tendency easily occurs; If surpass 8MPa, exist temperature of reaction to raise, the tendency that the yield of middle runnings reduces.

And then the volume ratio of hydrogen/stock oil is preferably 200～2000NL/L, be more preferably 300～1000NL/L.Herein, so-called " NL " refers to the capacity (L) of the hydrogen under standard state (0 ℃, 101325Pa).

In addition, the middle runnings being obtained by hydrogen treatment is more than 55%, to be preferably more than 58% with respect to the yield of the total mass of stock oil.In addition, the cetane value of the light oil containing in middle runnings is more than 75, is preferably more than 80, and yield point for-27.5 ℃ following, be preferably below-30.0 ℃.

In the manufacture method of liquid fuel of the present invention, the preferred silica alumina ratio of above-mentioned hyperstabilized y-type zeolite (silicon-dioxide is with respect to the mol ratio of aluminum oxide) is 20～50, is more preferably 30～40., if silica alumina ratio is less than 20, exist hydrocracking performance too high herein, the tendency that the yield of middle runnings reduces; If surpass 50, because hydrocracking performance is low, so the temperature of necessary rising hydrogenation exists hydrotreating catalyst to be easy to deteriorated tendency.

In addition, with respect to the total amount of above-mentioned carrier, above-mentioned hyperstabilized y-type zeolite preferably contains 0.5～6 quality %, more preferably contains 1～3 quality %.If USY zeolite lower than 0.5 quality % of the total amount of carrier, exists degrading activity to reduce, the tendency of the yield step-down of liquid fuel; If surpass 6 quality %, exist degrading activity too high, the tendency that the yield of middle runnings reduces.

And then above-mentioned hyperstabilized y-type zeolite can be prepared as follows: NaY type zeolite is carried out after ion-exchange with ammonium ion, process with high-temperature vapor, carry out dealuminzation.

In the manufacture method of liquid fuel of the present invention, above-mentioned amorphous solid acid preferably contains and is selected from one kind or two or more in amorphous aluminum silicide, amorphous silicon zirconium (amorphous silica-zirconia) and amorphous aluminium boron (amorphous alumina-boria).Herein, " amorphous " also referred to as amorphous, amorphousness, noncrystalline, even if refer to the ordered structure that has several short scopes, still lack as by X-ray diffraction, can determine and so on crystalline structure.Amorphous aluminum silicide can be used and for example contain 50～95 quality %SiO ₂, preferably contain 70～90 quality %SiO ₂material as composition.In addition, amorphous silicon zirconium can be used and for example contain 10～50 quality %SiO ₂, preferably contain 20～40 quality %SiO ₂material as composition.Amorphous aluminium boron can be used and for example contain 10～30 quality %A ₂lO ₃, preferably contain 13～28 quality %, more preferably contain 15～25 quality %A ₂lO ₃material as composition.

In addition, the quality m of the above-mentioned hyperstabilized y-type zeolite containing in above-mentioned carrier is preferably 1～60 with the ratio (n/m) of the quality n of above-mentioned amorphous solid acid, is more preferably 2～45, and more preferably 5～30.If mass ratio (n/m) is less than 1, exist degrading activity too high, the tendency that the yield of middle runnings reduces; If surpass 60, exist degrading activity to reduce, the tendency that the yield of middle runnings reduces.

In the manufacture method of liquid fuel of the present invention, above-mentioned active metal composition, with respect to the total amount of above-mentioned carrier, preferably contains 0.02～2 quality %, more preferably contains 0.05～1.5 quality %, more preferably contains 0.1～1.2 quality % as metal.Herein, active metal composition is with respect to the content of carrier total amount, if as metal lower than 0.02 quality %, exist the dehydrogenation of hydrotreating catalyst, Hydrogenation to reduce, the tendency that middle runnings reduces; If surpass 2 quality %, hydrotreating catalyst becomes expensive.Active metal composition is such as can be by existing method carrier bands such as impregnation method, ion exchange methods in carrier.

In the manufacture method of liquid fuel of the present invention, above-mentioned raw materials oil is preferably by the synthetic FT wax of manufacturing of fischer-tropsch (Fischer-Tropsch).In addition, FT wax preferably contains the above paraffins of 70 quality %.It should be noted that, in FT wax, contain oxygenatedchemicals and alkene as by product.

As oxygenatedchemicals, for example, comprise that carbonatoms is more than 16 alcohols with hydroxyl, particularly comprises hexadecanol, heptadecyl alcohol, stearyl alcohol etc. herein.In the present invention, the content of the oxygenatedchemicals of FT wax is below 10 quality %, is preferably below 5 quality %.If the oxygenatedchemicals in FT wax surpasses 10 quality %, exist hydrotreating catalyst deteriorated, the tendency of lifetime.

In addition, as alkene, for example, comprise that carbonatoms is more than 20, has a hydrocarbon of a unsaturated double-bond.In addition, the content of the alkene of FT wax is below 20 quality %, is preferably below 10 quality %.If the alkene in FT wax surpasses 20 quality %, in reaction system, be easy to part and cause that result exists the tendency of middle runnings elective reduction by the heat release of the hydrogenation generation of alkene.

In the manufacture method of liquid fuel of the present invention, above-mentioned middle runnings preferably contains the following oxygenatedchemicals of 0.1 quality %., if contained in middle runnings, surpass 0.1 quality % oxygenatedchemicals herein, the tendency that exists oxidative stability to reduce, therefore not preferred.

In the manufacture method of liquid fuel of the present invention, the active metal composition that contains amorphous solid acid and hyperstabilized y-type zeolite and formed by platinum or palladium due to the hydrotreating catalyst using, dehydrogenation, isomerization performance, hydrocracking performance and the Hydrogenation with hydro carbons, so hydrogen treatment can be carried out efficiently, can obtain middle runnings with high yield.In addition, the median size of hyperstabilized y-type zeolite be 0.2～1.0 μ m, take standard y-type zeolite benchmark degree of crystallinity as 1.02～1.10 and specific surface area be 700～790m ²/ g, therefore can improve degrading activity.And then the cetane value of the light oil containing in gained middle runnings is more than 75 and yield point is below-27.5 ℃, therefore can be preferably used as liquid fuel.

Embodiment

The manufacture method of the liquid fuel of one of embodiment of the present invention is described.

The hydrotreating catalyst using in the present invention can be manufactured as follows,, the active metal composition that carrier band is formed by platinum or palladium in the carrier that contains amorphous solid acid and hyperstabilized y-type zeolite and tackiness agent (binder), the median size of described hyperstabilized y-type zeolite is 0.2～1.0 μ m, take standard y-type zeolite benchmark degree of crystallinity as 1.02～1.10 and specific surface area be 700～790m ²/ g.

The hyperstabilized y-type zeolite of above-mentioned characteristic can be prepared as follows, for example, the NaY type zeolite of good crystallinity is carried out after ion-exchange with ammonium ion, with high-temperature vapor, processes, and carries out dealuminzation, by above-mentioned hyperstabilized being prepared.The silica alumina ratio of the USY zeolite obtaining is preferably 20～50.It should be noted that, generally, by hyperstabilized, the fine pore having except y-type zeolite itself is

outside the following fine pore structure that is known as fine pore, can also form fine pore and be 20～ new pore.Hyperstabilized y-type zeolite preferably contains 0.5～6 quality % with respect to the total amount of carrier.

As amorphous solid acid, can use and be selected from one kind or two or more in amorphous aluminum silicide, amorphous silicon zirconium and amorphous aluminium boron.Adding amorphous solid acid can make the ratio of the quality m of above-mentioned hyperstabilized y-type zeolite and the quality n of amorphous solid acid herein, is 1～60.

As tackiness agent, can use aluminum oxide, silicon-dioxide, titanium dioxide, magnesium oxide etc.As the use level of tackiness agent, the total amount of carrier of take is benchmark, is preferably 5～99 quality %, is more preferably 20～99 quality %.

Active metal composition, with respect to the total amount of carrier, preferably contains 0.02～2 quality % as metal.

Herein, carrier is manufactured as follows, by the mixture that mixes hyperstabilized y-type zeolite, amorphous solid acid and tackiness agent with single-lead-screw extruding briquetting machine extrusion molding for for example diameter be 1/16 inch of (about 1.6mm), length after to be 5mm cylindric, at 450～550 ℃, burn till, thus manufacture.And then, by such as impregnation method and ion exchange method etc., make the carrier carried platinum or the palladium that obtain, manufacture hydrotreating catalyst.

The hydrogenation treatment method of<paraffins>

Hydrogenation treatment method of the present invention is as follows, under the existence of above-mentioned hydrotreating catalyst, in temperature, is that 200～350 ℃, liquid hourly space velocity are 0.1～5.0h ^-1and under the hydrogen dividing potential drop condition that is 0.5～8MPa, to take the stock oil that the paraffins of carbonatoms 20～100 is main component, carry out hydrogen treatment, obtain processing oil.It should be noted that, hydrogen/oil ratio is not particularly limited, but is preferably 200～2000NL/L.

As stock oil, preferably by fischer-tropsch, synthesize the FT wax of manufacturing, contain the above paraffins of 70 quality %.It should be noted that, FT wax can contain 10 quality % following oxygenatedchemicals and/or the following alkene of 20 quality % as by product.

Herein, the hydrogen treatment of paraffins can be used existing fixed-bed reactor.

The manufacture method of<liquid fuel>

By utilizing the air distillation of distillation tower etc., the processing oil content being obtained by hydrogen treatment can be fractionated into the cut of hope, for example naphtha fraction (145 ℃ of following cuts of boiling point), middle runnings (cuts that boiling point is 145～360 ℃), light oil (260～360 ℃ of boiling points).Thus, can manufacture liquid fuel.

Embodiment

In the aqueous sodium hydroxide solution of 6.685kg 41.95 quality %, add while stirring the sodium aluminate aqueous solution of 1.614kg39 quality % (as composition, to contain 17 quality %Na ₂o, 22 quality %Al ₂o ₃.Identical below.)。And then, add while stirring No. 3 water glass of 13.053kg (as composition, to contain 24 quality %SiO this mixing solutions ₂, 7.7 quality %Na ₂o.Identical below.) in, obtain crystal seed composition.And then, crystal seed composition was stirred after 30 minutes, in 30～35 ℃ standing 13 hours, obtain the crystal seed of 21.351kg.

Then, in the pure water of 5.327kg, add the aluminum sulfate aqueous solution of 18.244kg 23.6 quality % (as composition, to contain 7 quality %Al ₂o ₃.Identical below.), be uniformly mixed, and then, add No. 3 water glass of 22.947kg, be uniformly mixed, make crystal solution.In this crystal solution, add the above-mentioned crystal seed of 21.351kg, be mixed to fully evenly, under room temperature, stir 3 hours, make it slaking, obtain reaction mixture.

Reaction mixture is kneaded into after solid shape by colloidal mill, packs in crystallizer tank, carry out slaking 40 hours in 95 ℃, make y-type zeolite crystallization.After slaking finishes, crystallisation by cooling groove, takes out crystallisate (being in fact the crude product of y-type zeolite), filters successively, cleans, is dried, and obtains the NaY type zeolite a (below also referred to as " NaY (a) ") of about 7.3kg.Obtain median size, degree of crystallinity, lattice parameter, silica alumina ratio, the specific surface area of NaY (a).Above-mentioned proterties is shown in table 1.

[table 1]

	NaY(a)	NaY(b)	NaY(c)
				Degree of crystallinity (%)	1.05	1.04	0.86
Lattice parameter (A)	24.67	24.66	24.66
				Silica alumina ratio	5.0	5.1	5.1
Specific surface area (m ²/g)	728	730	698
				Median size (μ m)	0.3	1.0	0.3

And then, the NaY type zeolite a obtaining is carried out to ion-exchange with ammonium sulfate, by steam treatment, obtain HY zeolite.This HY zeolite is carried out to ion-exchange with ammonium sulfate, by steam treatment, obtain thick USY zeolite.Then, above-mentioned thick USY zeolite is carried out to acid treatment with sulfuric acid, obtain hyperstabilized y-type zeolite a (following, also referred to as " USY (a) ").Obtain median size, degree of crystallinity, lattice parameter, silica alumina ratio, the specific surface area of USY (a).Above-mentioned proterties is shown in table 2.

[table 2]

	USY(a)	USY(b)	USY(c)
				Degree of crystallinity (%)	1.05	1.03	0.83
Lattice parameter (A)	24.35	24.34	24.34
				Silica alumina ratio	40.1	40.3	40.2
Specific surface area (m ²/g)	782	730	702
				Median size (μ m)	0.3	1.0	0.3

Then, the sial (silica-alumina) that the USY that 30g is obtained (a) and 270g silica/alumina mole ratio are 6.1 and 700g are after the aluminum oxide mixing of tackiness agent, pass through single-lead-screw extruding briquetting machine, extrusion molding is that diameter is that 1/16 inch of (about 1.6mm), length are after to be 5mm cylindric, in air, burn till 1 hour in 500 ℃, obtain carrier.The aqueous solution of chloroplatinic acid that to make as platinum be the amount of 0.5 quality % is impregnated in gained carrier, and then, by its in 120 ℃ dry 3 hours and burn till 1 hour in 500 ℃, manufacture thus hydrotreating catalyst A (following, also referred to as " catalyst A ".Following catalyzer is also identical.)。The composition of hydrotreating catalyst A is shown in table 3.

[table 3]

	Catalyst A	Catalyst B	Catalyzer C	Catalyzer D	Catalyzer E	Catalyzer F
							USY(a)(g)	30	20	30
USY(b)(g)				30
							USY(c)(g)					30	20
Sial (g)	270
							Aluminium boron (g)		570				570
Aluminum oxide (g)	700	410	970	970	970	410
							Platinum (g)	5	5	5	5	5	5

Aspect mixing as the aluminum oxide of tackiness agent at the aluminium boron (alumina-boria) that is 5.7 using 20g USY (a) and 570g aluminum oxide/boron oxide mol ratio and 410g, A is different from hydrotreating catalyst.The composition of hydrotreating catalyst B is shown in table 3.

Aspect mixing at the aluminum oxide using 30g USY zeolite (a) and 970g as tackiness agent, A is different from hydrotreating catalyst.The composition of hydrotreating catalyst C is shown in table 3.

Use the commercially available NaY type zeolite of 7kg (for example Zeolyst company system, CBV100.Below, be called " NaY (b) "), similarly process with the manufacture method of hydrotreating catalyst A, manufacture hyperstabilized y-type zeolite b (below also referred to as " USY (b) ").Degree of crystallinity, lattice parameter, silica alumina ratio, the specific surface area of obtaining respectively NaY (b), USY (b), above-mentioned proterties is shown in table 1, table 2.

And then the USY that 30g is obtained (b) and 970g mix as the aluminum oxide of tackiness agent, similarly process with the manufacture method of hydrotreating catalyst A, manufacture hydrotreating catalyst D.The composition of hydrotreating catalyst D is shown in table 3.

In 10.621kg 22.76 quality % aqueous sodium hydroxide solutions, add while stirring 1.391kg 39 quality % sodium aluminate aqueous solutions.And then, above-mentioned mixing solutions is added in No. 3 water glass of 11.250kg while stirring, obtain crystal seed composition.And then, stir crystal seed composition after 30 minutes, under room temperature standing 20 hours, make it after slaking, in 60 minutes, be warming up to 80 ℃, be cooled to immediately after 50 ℃, filter, clean, obtain the crystal seed of 9.50kg.

Then, at the pure water of 28.539kg, add the 7.53kg 47.0 quality % silicon-dioxide aqueous solution and No. 3 water glass of 19.978kg, be uniformly mixed.And then, in above-mentioned solution, add 5.124kg crystal seed, be uniformly mixed, add 6.691kg sodium aluminate aqueous solution, be mixed to fully evenly, under room temperature, stir 3 hours, make it slaking, obtain reaction mixture.

After reaction mixture is pulverized with microjet clarifixator (Microfluidizer), pack in crystallizer tank, at 95 ℃, carry out slaking 10～100 hours (present embodiment is 40 hours), make y-type zeolite crystallization.After slaking finishes, crystallisation by cooling groove, takes out crystallisate (being essentially the crude product of y-type zeolite), filters successively, cleans, is dried, and obtains the NaY type zeolite c (following, also referred to as " NaY (c) ") of about 7.0kg.Obtain median size, degree of crystallinity, lattice parameter, silica alumina ratio, the specific surface area of NaY (c).Above-mentioned proterties is shown in table 1.

And then, the NaY obtaining (c) is similarly processed with the manufacture method of hydrotreating catalyst A, manufacture hyperstabilized y-type zeolite c (following, also referred to as " USY (c) ").Degree of crystallinity, lattice parameter, silica alumina ratio, the specific surface area of obtaining USY (c), above-mentioned proterties is shown in table 2.

And then the USY that 30g is obtained (c) and 970g mix as the aluminum oxide of tackiness agent, similarly process with the manufacture method of hydrotreating catalyst A, manufacture hydrotreating catalyst E.The composition of hydrotreating catalyst E is shown in table 3.

Aspect mixing as the aluminum oxide of tackiness agent at the aluminium boron that is 5.7 using 20g USY (c) and 570g aluminum oxide/boron oxide mol ratio and 410g, E is different from hydrotreating catalyst.The composition of hydrotreating catalyst F is shown in table 3.

The manufacture method of<hydrogen treatment and liquid fuel>

(embodiment 1)

First, the hydrotreating catalyst A of 100ml is filled in fixed-bed reactor, under 340 ℃, the hydrogen stream of hydrogen dividing potential drop 3MPa, reduces after hydrotreating catalyst A, as stock oil, to synthesize the FT wax of manufacturing by fischer-tropsch, carry out hydrogen treatment.In FT wax, contain 85 quality % as the paraffins (it should be noted that, normal paraffin is that 81 quality %, different alkane are 4 quality %) of the carbonatoms 20～89 of main component, 3 quality % oxygenatedchemicals, the 10 quality % alkene as by product.

In hydrocracking reaction, making hydrogen dividing potential drop is that the liquid hourly space velocity of 3MPa, raw material is 2.0h ^-1, regulate temperature (temperature of reaction) to make the 80 quality % that 360 ℃ of following degradation productions of boiling point are raw material, rate of decomposition is 80%.Temperature of reaction is now 288 ℃ (referring to table 4).By distillation, degradation production is separated into petroleum naphtha (boiling point is for～145 ℃), lam-oil (boiling point is 145～260 ℃), light oil (boiling point is 260～360 ℃), obtains the yield of each cut, the above results is shown in table 4.Calculate middle runnings yield as the summation of lam-oil yield and light oil yield.In addition, as the characteristic of light oil, according to the method for recording in JIS-K-2269, JIS-K-2280, obtain respectively yield point and cetane value, the above results is shown in table 4.And then, the oxygenatedchemicals containing in middle runnings is utilized to the determination of elemental analysis of LECO method, to obtain oxygen and remove rate, the above results is shown in table 4.

(embodiment 2, comparative example 1～4)

Embodiment 2, comparative example 1～4, use respectively hydrotreating catalyst B～F replace hydrotreating catalyst A aspect, different from embodiment 1.It should be noted that, in embodiment 2, comparative example 1～4, the rate of removing of the yield point of the temperature of reaction that rate of decomposition is 80%, the yield of middle runnings, light oil and cetane value, oxygenatedchemicals is shown in table 4.

(comparative example 5)

Different from embodiment 2 aspect use catalyzer C replacement catalyst B.Temperature of reaction is identical with embodiment 2.The rate of removing of the yield of temperature of reaction, rate of decomposition, middle runnings, the yield point of light oil and cetane value, oxygenatedchemicals is shown in table 4.

[table 4]

From the above, by using the crystallized silicon aluminate that amorphous solid is sour and particle diameter is little and degree of crystallinity is high, can from the paraffins that contains oxygenatedchemicals and alkene, obtain middle runnings with high yield, manufacture the light oil that yield point is low, cetane value is high, remove efficiently oxygenatedchemicals simultaneously.

The present invention is not limited to above-mentioned embodiment, can in the scope that does not change main points of the present invention, change, for example, part or all of the respective embodiments described above and variation be combined and the situation that forms the manufacture method of liquid fuel of the present invention is also included within the scope of claim of the present invention.

For example, in the manufacture method of the liquid fuel of above-mentioned embodiment, also can use silicon zirconium (Silica-Zirconia) as amorphous solid acid.

Claims

1. a manufacture method for liquid fuel, described manufacture method is under the existence of hydrotreating catalyst, in temperature, is that 200～350 ℃, liquid hourly space velocity are 0.1～5.0h ^-1and under the hydrogen dividing potential drop condition that is 0.5～8MPa, to take the stock oil that the paraffins of carbonatoms 20～100 is main component, carry out hydrogen treatment, obtain processing after oil, this processing oil content is heated up in a steamer, obtain yield with respect to the total mass of above-mentioned raw materials oil and be containing cetane value is more than 75 and the yield point middle runnings that is-27.5 ℃ of following light oil more than 55%, simultaneously, described stock oil is to synthesize by fischer-tropsch the FT wax of manufacturing

It is characterized in that, the described hydrotreating catalyst active metal composition that carrier band is formed by platinum or palladium in the carrier that contains amorphous solid acid and hyperstabilized y-type zeolite, dehydrogenation, isomerization performance, hydrocracking performance and the Hydrogenation with hydro carbons, the median size of described hyperstabilized y-type zeolite is 0.2～1.0 μ m, take standard y-type zeolite benchmark degree of crystallinity as 1.02～1.10 and specific surface area be 700～790m ²/ g.

2. the manufacture method of liquid fuel as claimed in claim 1, is characterized in that, the silica alumina ratio of described hyperstabilized y-type zeolite is 20～50.

3. the manufacture method of the liquid fuel as described in any one in claim 1 and 2, is characterized in that, with respect to the total amount of described carrier, and the described hyperstabilized y-type zeolite that contains 0.5～6 quality %.

4. the manufacture method of liquid fuel as claimed in claim 1 or 2, is characterized in that, described hyperstabilized y-type zeolite is by NaY type zeolite is carried out after ion-exchange with ammonium ion, processes, then carry out dealuminzation and prepare with high-temperature vapor.

5. the manufacture method of liquid fuel as claimed in claim 1 or 2, is characterized in that, described amorphous solid acid contains and is selected from one kind or two or more in amorphous aluminum silicide, amorphous silicon zirconium and amorphous aluminium boron.

6. the manufacture method of liquid fuel as claimed in claim 1 or 2, is characterized in that, the ratio of the quality m of the described hyperstabilized y-type zeolite containing in the quality n of described amorphous solid acid and described carrier is that n/m is 1～60.

7. the manufacture method of liquid fuel as claimed in claim 1 or 2, is characterized in that, with respect to the total amount of described carrier, and as metal, the described active metal composition that contains 0.02～2 quality %.

8. the manufacture method of liquid fuel as claimed in claim 1 or 2, is characterized in that, described FT wax contains the above paraffins of 70 quality %.

9. the manufacture method of liquid fuel as claimed in claim 1 or 2, is characterized in that, described FT wax contains the following oxygenatedchemicals of 10 quality % and/or the following alkene of 20 quality %.

10. the manufacture method of liquid fuel as claimed in claim 1 or 2, is characterized in that, described middle runnings contains the following oxygenatedchemicals of 0.1 quality %.